US4208316A - Hydrophobic precipitated silicic acid and compositions containing same - Google Patents

Hydrophobic precipitated silicic acid and compositions containing same Download PDF

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US4208316A
US4208316A US05/920,515 US92051578A US4208316A US 4208316 A US4208316 A US 4208316A US 92051578 A US92051578 A US 92051578A US 4208316 A US4208316 A US 4208316A
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silicic acid
din
precipitated silicic
hrs
hydrophobic
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Peter Nauroth
Heinz Esch
Robert Kuhlmann
Rudolf Bode
Arthur Reisert
Harald Buhler
Gunter Turk
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Evonik Operations GmbH
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Deutsche Gold und Silber Scheideanstalt
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the invention relates to a hydrophobic precipitated silicic acid and its use as a reinforcing filler in synthetic or natural plastic masses that may be hardened to elastomers.
  • the invention further relates to products made from the reinforced elastomers.
  • Fillers are solid substances which are generally of inorganic origin and varied composition, the particles of which may range from fine to rough grained and of varied shape and which are added to a chemical industrial product in order to improve certain characteristics.
  • the loss at drying may range from 2.5 to 0.0%.
  • the conductivity of the hydrophobic precipitation silicic acid of the invention may preferably range from 50 to 300 ⁇ S.
  • the wettability with water may preferably range from 0 to 0.05.
  • a further object of the present invention resides in a process for the production of hydrophobic precipitated silicic acid, which comprising providing an original aqueous alkaline suspension containing a hydrophilic silicic acid with the following physico-chemical characteristics (obtained after separation from the precipitated suspension, intensive washing with water and extended drying of the hydrophylic precipitated silicic acid):
  • FIG. 1 shows a plot of specific dielectric resistivity versus temperature.
  • the original aqueous alkaline suspension of the hydrophylic precipitated silicic acid may be obtained as follows:
  • organo silicon compounds include those which may be represented by the general formula:
  • R is the same or different monovalent, optionally substituted and/or polymeric, hydrocarbon radicals, a is 1 or 2, and Z is halogen, hydrogen or a radical of the formula: --OH, --OR, --NRX, --ONR 2 , --SR, --OOCR, --O--, --N(X)-- or --S--, wherein R always has the above stated meaning and X is hydrogen or has the same meaning as R.
  • organo silicon compounds examples include hexamethyl disilazan, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, triorganosilyl mercaptans such as trimethylsilane mercaptan, triorganosilylacylates such as vinyldimethylacetoxysilane, triorganosilylamines such as trimethylsilylisoproplyamine, trimethylsilylethylamine, dimethylphenylsilylpropylamine and vinyldimethylsilylbutylamine, triorganosilylaminoxy compounds such as diethylaminoxytrimethylsilane and diethylaminoxydimethylphenyl silane; furthermore hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-diphenyltetramethyldisiloxane and 1,3-diphenylhexamethyldisilazane.
  • organosilicon compounds which may be reacted within the scope of the invention with the original aqueous alkaline suspension of hydrophylic silicic acid are the following: dimethyldichlorosilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, vinylmethyldimethoxysilane and octamethylcyclotetrasiloxane, and/or dimethylpolysiloxanes with 2 to 12 siloxane units per molecule and always containing an Si-bound hydroxyl group in the terminal units.
  • Mixtures of different organosilicon compounds may also be used according to the invention to react with the hydrophibic silicic acid present in the original aqueous precipitated suspension.
  • dimethylchlorosilane may be used as the hydrophobic producing agent.
  • hydrophobic producing agent is meant any of the above mentioned organosilion compounds or their art recognized equivalents.
  • organosilicon compounds which are reacted with aqueous alkaline original suspensions of hydrophylic precipitated silicic acid, according to the invention are used preferably in quantities of 5 to 30% by weight, relative to the weight of the precipitated silicic acid reacted therewith.
  • a further object of the invention is the use of the hydrophobic precipitated silicic acid of the invention as a reinforcing filler in natural or synthetic plastic masses hardenable into elastomers; and especially in diorganopolysiloxane elastomeric polymers.
  • the hydrophobic precipitated silicic acid of the invention may be used in a single component, silicon rubber hardenable mass for sealing or caulking of cracks and the like.
  • One component and two component hardenable compositions are known in the art as shown for example in U.S. Pat. Nos. 3,122,516, 3,464,951 and 3,334,067 and in British Pat. No. 1,110,429. These prior art documents are relied on herein for their disclosures and incorporated.
  • the filler of the invention may be used in organopolysiloxane elastomers, hardenable at room temperature as for example, preferably in a two-component silicon printing composition.
  • the hydrophobic precipitated silicic acid may also be used in hot vulcanizing diorganopolysiloxane elastomers. They may be used for example, as a cable insulation material.
  • All diorganopolysiloxanes may be used for purposes of the invention which hitherto were used or could be used as the basis for plastic masses hardenable or hardening into organopolysiloxane elastomers at room temperature (RTV) or only slightly higher temperature (LTV) or high temperature (HTV). They are known in the art and may be represented for example, by the general formula:
  • R is the same or different monovalent, optionally substituted and/or polymeric hydrocarbon radicals
  • Z is a hydroxyl group, hydrolyzable group and/or hydrolyzable atom, or in case of there being only masses hardenable at slightly elevated temperature, alkenyl groups
  • n is 1,2 or 3 and x a whole number with a value of at least 1.
  • hydrocarbon radical R examples include alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl and octyl radicals; alkenyl radicals such as the vinyl, allyl, ethylallyl and butadienyl radical; and aryl radicals such as phenyl and tolyl.
  • subtituted hydrocarbon radicals R are especially halogenated hydrocarbon radicals, such as 3,3,3-trifluoropropyl, chlorophenyl and bromotolyl; and cyanoalkyl radicals such as beta-cyanoethyl.
  • polymeric substituted and unsubstituted hydrocarbon radicals R are polystyrl, polyvinylacetyl, polyarylyl, polymethacrylyl and polyacrylic nitrilyl radicals bound to silicon by way of carbon.
  • radicals R consist preferably of methyl groups largely because of easier accessability. Any remaining radicals R, are preferably vinyl and/or phenyl groups.
  • Z is generally a hydrolizable group.
  • groups are amino, amido, aminoxy, oxime, alkoxy, alkoxyalkoxy--(for example, CH 3 OCH 2 CH 2 O--), alkenyloxy-(for example, H 2 C ⁇ (CH 3 )CO--), acyloxy and phosphato groups.
  • acetoxy groups are preferred as the Z acyloxy group, chiefly because of their easier accessability.
  • Z is an oxime group such as those of the formula --ON ⁇ C(CH 3 ) (C 2 H 5 ), excellent results will be achieved.
  • hydrolyzable atoms Z are halogen and hydrogen atoms.
  • alkenyl groups Z are especially vinyl groups. It should be noted that the same or different Z groups may be bound to an Si-atom. Mixtures of different diorganopolysiloxanes may be used.
  • masses hardenable to elastomers especially with exclusion of water, and in the case of admission of water, masses hardening to elastomers at room temperature can be produced from the hydrophobic silicic acid described herein, by mixing the diorganopolysiloxanes and possibly additional substances at room temperature or at only slightly elevated temperature, optionally after addition of crosslinking agents. This mixing may be accomplished in any known manner, as for example in mechanical mixing devices.
  • the fillers used according to the invention are used in quantities of 5 to 50% by weight, related to the total weight of the masses hardenable to elastomers.
  • the fillers used according to the invention are used in quantities of 5 to 50% by weight, related to the total weight of the masses hardenable to elastomers.
  • from 5 to 50% by weight may be used.
  • RTV organopolysiloxane elastomers from 5 to 35 preferably 5 to 25% by weight may be used.
  • organic peroxides such as for example, bis-2.4 dichlorobenzoyl peroxide, benzoylperoxide, dicumylperoxide, tertiary butylperbenzoate or tert. butylperacetate as a crosslinking agent.
  • organic substituents consist of methyl, ethyl, phenyl, trifluoromethyl phenyl[F 3 CC 6 H 4 ], or trimethyl silmethyl radicals [(CH 3 ) 3 SiCH 2 --], for example, dimethyl, diethyl, phenyl, methyl, phenylethyl, ethylmethyl, trimethylsilylmethylene methyl, trimethylsilylmethylene ethyl, trifluoromethylphenylmethyl, or trifluoromethylphenylethyl siloxane or copolymerisates of such compounds.
  • polymerisates may contain limited quantities of diphenylsiloxane, bis-trimethylsilyl methylene siloxane, bis-trifluoromethyl phenylsiloxane units as well as siloxanes with units of the formula RSiO 1 .5 and R 3 SiO 0 .5, whereby R represents one of the above radicals.
  • crosslinking agents are particularly silanes of the general formula:
  • R has the meaning stated above, Z', is a hydrolizable group and/or a hydrolizable atom and t is 3 or 4.
  • Z' is a hydrolizable group and/or a hydrolizable atom and t is 3 or 4.
  • the previously mentioned examples for hydrolizable groups Z and hydrolizable atoms Z apply equally for the hydrolizable groups Z' and the hydrolizable atoms Z'.
  • silanes of the above formula are methyl triacetoxysilane, isopropyl triacetoxysilane, isopropoxy triacetoxysilane, vinyltriacetoxysilane, methyl trisdiethylamino oxysilane, methyl tris (-cyclohexylamino)-silane, methyltris (-diethylphosphate)-silane and methyltris (-methylethylketoximo)-silane.
  • polysiloxanes which contain at least 3 Z' groups or atoms per molecule, may also be used instead of or mixed with silances of the above formula, whereby the silicon valencies not saturated by Z' group or atoms, are saturated by siloxane oxygen atoms and optionally R groups.
  • crosslinking agents of the latter type are the polyethylsilicates with an SiO 2 content of about 40% by weight, hexaethoxydisiloxane and methane polysiloxane.
  • condensation catalysts are tin salts of fatty acids, such as dibutyltindilaurate, dibutyltindiacetate and tin-(II)-octoate.
  • organopolysiloxanes which contain on an average at least 3 Si-bound hydrogen atoms per molecule, such as methanepolysiloxane, in the presence of catalysts, such as platinum-(IV)-chloricacid, promoting the addition of alkenyl group to Si-bound hydrogen.
  • catalysts such as platinum-(IV)-chloricacid
  • the masses hardenable into elastomers beside diorganopolysiloxanes, precipitated silicic acid according to the invention, crosslinking agents and crosslinking catalysts, may optionally contain conventional fillers used in masses hardenable into elastomers.
  • Such substances are fillers with a surface area less than 50 m 2 /g, such as quartz powder, diatomaceous earth, zirconium silicate and calcium carbonate, untreated, pyrogenic silicondioxide, organic resins such as polyvinylchloride powder, organopolysiloxane resins, fibrous fillers such as asbestos, glass fibers and organic fibers, pigments, soluble dyes, aromatics, corrosion inhibitors, agents stabilizing the masses against the effect of water, such as acetic acid anhydride, agents for delaying or retarding the hardening or curing, such a benzotriazole and softeners, such as dimethylpolysiloxanes, endblocked by trimethyl siloxy groups.
  • organic resins such as polyvinylchloride powder, organopolysiloxane resins
  • fibrous fillers such as asbestos, glass fibers and organic fibers, pigments, soluble dyes, aromatics, corrosion inhibitors
  • agents stabilizing the masses against the effect of water
  • the above enumerated combination of physico-chemical data relating to the hydrophobic precipitated silicic acid of the invention because of its excellent dispersability will lead to a highly effective reinforcing and strengthening filler.
  • the aquilibrium moisture content clearly reduced as compared to known precipitated silicic acids, produces advantages during processing, for example in the case of pressureless vulcanization where a cured product is obtained with fewer bubbles as compared to the use of the known hydrated precipitated silicic acid.
  • the electrolyte content combined with the low moisture content leads to good electrical characteristics in the cured product.
  • the hydrophobic precipitated silicic acid of the invention on the basis of its low water content, exhibits advantages in storage stability of the un-cured masses.
  • a part of the suspension is filtered off, washed until "poor in electrolyte,” subsequently dryed in the drying cabinet at 105° C. up to constant weight and is ground in a disk mill.
  • a sample of 4.0 silicic acid is heated in 50 ml fully desalinated water in a 150 ml glass beaker and is boiled for one minute while stirring. Subsequently, the suspension is transferred into a 100 ml measuring flask, is cooled down, and is then filled up to the mark with fully desalinated water. After agitating, the measuring cell of the conductivity measuring device is first preliminarily flushed with the suspension to be measured and is then filled or the measuring cell is submerged into the suspension. The electric conductivity is read from the measuring device and the temperature of the suspension is determined during the measurement.
  • the hydrophobic precipitated silicic acid thus obtained has the following physico-chemical characteristics:
  • hydrophobic silicic acid 0.2 g are placed with 50 ml of distilled water into a 250 ml vibrating funnel and are vibrated at the highest speed for 1 minute with the help of a Turbula-mixer.
  • the maximum or time-dependent moisture absorption of silicic acids is determined in dependence on the temperature and of the relative humidity of the air.
  • a silicic acid sample of about 2.5 g is weighed in up to 0.1 mg. exactly, into a dry calibrated weighing bottle and is dried for 2 hours at 105° C. After cooling, the weight is determined on an analytical balance. Subsequently, the open weighing bottle is kept with the sample in a conditioning cabinet at a predetermined temperature and relative humidity of the air. One may then either determine a moisture absorption/time diagram or the maximum moisture absorption.
  • hydrophobic precipitated silicic acid of the invention according to example 2 is tested as a reinforcing filler and thixotroping agent in a 1-component silicon rubber crack-sealing mass (cold curing).
  • HDK H2000 R is a highly dispersed silicic acid, which is produced by flame-hydrolysis from volatile silicon masses and is subsequently hydrophobed by reaction with organosilanes. It is therefore tightly covered with trimethylsilyl groups on the surface and has the following physico-chemical characteristics:
  • Aerosil 150 R is a pyrogenically produced silicic acid with the following physico-chemical characteristics.
  • the incorporation of the silicic acid takes place after the addition of the crosslinking agent in an evacuated planetary type mixer.
  • Aerosil 150 may only be incorporated up to 8% into the 1-component sealing mass. A higher degree of filling leads to a mass difficult to process. The level of the machanical data attainable at a degree of 8% filler content corresponds to the customary status of the prior art.
  • hydrophobic precipitated silicic acid of example 4 according to the invention is incorporated as reinforcing filler in hot vulcanized silicon rubber and is checked for the electric volume resistance of the cured goods produced therewith.
  • hot-vulcanizing silicon rubber is also used as a high grade cable insulating material.
  • highly active pyrogenic silicic acid is conventionally used as a filler because of it unity and its favorable dielectric characteristics. It has been known, that the insulating characteristics are improved further, whenever the fully cured compounds are further subjected to an extended tempering process (at least 6 hours) at elevated temperatures (200° C.).

Abstract

Hydrophobic precipitated silicic acid is disclosed and its use as a reinforcing filler in plastic masses which are hardenable to form elastomers.

Description

The invention relates to a hydrophobic precipitated silicic acid and its use as a reinforcing filler in synthetic or natural plastic masses that may be hardened to elastomers. The invention further relates to products made from the reinforced elastomers.
Fillers are solid substances which are generally of inorganic origin and varied composition, the particles of which may range from fine to rough grained and of varied shape and which are added to a chemical industrial product in order to improve certain characteristics.
It is an object of the present invention to provide a hydrophobic precipitated silicic acid, which has the following characteristics:
______________________________________                                    
BET-surface        m.sup.2 /g 110 ± 40                                 
Average size of the                                                       
 primary particles mμ(nm)  15- 22                                      
 from EM records                                                          
Loss at drying accord-                                                    
 ing to DIN 55 921 %          <2.5                                        
 after 2 hrs at 105° C.                                            
Loss at red heat (related                                                 
 to the substance dried                                                   
                   %          5.5 ± 1.5                                
 2 hrs at 105° C.) accord-                                         
 ing to DIN 55 921                                                        
pH value (in 5% aqueous                                                   
 methanolic suspen-           7.5 ± 1.0                                
 sion) according to                                                       
 DIN 53200                                                                
Conductivity (in 4%                                                       
 aqueous methanolic                                                       
                   μS      <600                                        
 suspension)                                                              
Tamping density of the                                                    
 unaerated substance                                                      
                   g/l        130 ± 40                                 
 according to DIN 53                                                      
 194                                                                      
Wettability with water        <0.1                                        
Carbon content     %          2.5 ± 0.6                                
Water absorption at 30°                                            
 and 30% RH (relative                                                     
                   %          1.2 ± 0.4                                
 humidity)                                                                
 at 30° and 70% RH                                                 
 (relative humidity)                                                      
                   %          1.5 ± 0.5                                
______________________________________
In a preferred embodiment of the hydrophobic precipitated silicic acid of the invention, the loss at drying may range from 2.5 to 0.0%. The conductivity of the hydrophobic precipitation silicic acid of the invention may preferably range from 50 to 300 μS. The wettability with water may preferably range from 0 to 0.05.
A further object of the present invention resides in a process for the production of hydrophobic precipitated silicic acid, which comprising providing an original aqueous alkaline suspension containing a hydrophilic silicic acid with the following physico-chemical characteristics (obtained after separation from the precipitated suspension, intensive washing with water and extended drying of the hydrophylic precipitated silicic acid):
______________________________________                                    
BET-surface according                                                     
                   m.sup.2 /g 160 ± 40                                 
 to DIN 66 131                                                            
Average size of the                                                       
 primary particles mμ(nm)  14- 22                                      
 from EM records                                                          
Loss in weight at dry-                                                    
 ing according to  %          2.5-4.0                                     
 DIN 55 921 after                                                         
 2 hrs at 105° C.                                                  
Loss in weight at red                                                     
 heat (related to                                                         
 substance dried 2 %          3.5 ± 1.0                                
 hrs at 105° C.) accord-                                           
 ing to DIN 55 921                                                        
pH value (in 5% aqueous                                                   
 suspension) accord-          7.0-8.5                                     
 ing to DIN 53 200                                                        
Conductivity in 4%                                                        
 aqueous suspension                                                       
                   μ S     <600                                        
Tamping density of the                                                    
 unaerated substance                                                      
                   g/l        140 ± 40                                 
 according to DIN 53                                                      
 194                                                                      
SO.sub.3 content (relating to                                             
 substance dried 2 hrs                                                    
                   %          <0.3                                        
 at 105° C.)                                                       
Na.sub.2 O content (relative to                                           
 substance dried 2 hrs                                                    
                   %          <0.3                                        
 at 105° C.)                                                       
______________________________________
and introducing into the aqueous alkaline suspension as described above, a hydrophobic producing agent while maintaining an alkaline pH value in the original suspension to obtain a mixture, stirring the mixture thus obtained, separating the hydrophobic precipitated silicic acid thus obtained, drying for a sufficient duration, tempering the product thus obtained for 60 to 180 minutes, preferably 70 to 130 minutes at a temperature of 200° to 400° C. and thereafter grinding it to produce a finely divided product with the indicated average particle size range.
The invention is illustrated by FIG. 1 which shows a plot of specific dielectric resistivity versus temperature.
The original aqueous alkaline suspension of the hydrophylic precipitated silicic acid may be obtained as follows:
1 part by volume of water is introduced into a suitable reaction vessel. From 0.15 to 0.25 parts by volume of a sodium silicate solution (ratio SiO2 :Na2 O=3.5 and 26% SiO2) and 0.015 to 0.025 parts by volume of H2 SO4 (96% conc.) are slowly added to the reaction vessel while stirring, whereby an alkaline pH value is maintained in the mixture during the addition. After completing the addition of sodium silicate and H2 SO4, the pH value of the suspension obtained is in the weakly alkaline range.
The agents which are used according to the invention to create the hydrophobic effect and which are reacted with the original hydrophylic silicic acid suspended in the aqueous phase to convert it to a hydrophobic product are organo silicon compounds. Included among the suitable organo silicon compounds are those which may be represented by the general formula:
(R.sub.3 Si).sub.a Z
wherein R is the same or different monovalent, optionally substituted and/or polymeric, hydrocarbon radicals, a is 1 or 2, and Z is halogen, hydrogen or a radical of the formula: --OH, --OR, --NRX, --ONR2, --SR, --OOCR, --O--, --N(X)-- or --S--, wherein R always has the above stated meaning and X is hydrogen or has the same meaning as R.
Examples of suitable organo silicon compounds are hexamethyl disilazan, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, triorganosilyl mercaptans such as trimethylsilane mercaptan, triorganosilylacylates such as vinyldimethylacetoxysilane, triorganosilylamines such as trimethylsilylisoproplyamine, trimethylsilylethylamine, dimethylphenylsilylpropylamine and vinyldimethylsilylbutylamine, triorganosilylaminoxy compounds such as diethylaminoxytrimethylsilane and diethylaminoxydimethylphenyl silane; furthermore hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-diphenyltetramethyldisiloxane and 1,3-diphenylhexamethyldisilazane.
Additional examples for organosilicon compounds, which may be reacted within the scope of the invention with the original aqueous alkaline suspension of hydrophylic silicic acid are the following: dimethyldichlorosilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, vinylmethyldimethoxysilane and octamethylcyclotetrasiloxane, and/or dimethylpolysiloxanes with 2 to 12 siloxane units per molecule and always containing an Si-bound hydroxyl group in the terminal units.
Mixtures of different organosilicon compounds may also be used according to the invention to react with the hydrophibic silicic acid present in the original aqueous precipitated suspension.
In a preferred embodiment of the invention dimethylchlorosilane may be used as the hydrophobic producing agent. By the term hydrophobic producing agent is meant any of the above mentioned organosilion compounds or their art recognized equivalents.
The organosilicon compounds which are reacted with aqueous alkaline original suspensions of hydrophylic precipitated silicic acid, according to the invention are used preferably in quantities of 5 to 30% by weight, relative to the weight of the precipitated silicic acid reacted therewith.
A further object of the invention is the use of the hydrophobic precipitated silicic acid of the invention as a reinforcing filler in natural or synthetic plastic masses hardenable into elastomers; and especially in diorganopolysiloxane elastomeric polymers. For example, in a preferred embodiment the hydrophobic precipitated silicic acid of the invention may be used in a single component, silicon rubber hardenable mass for sealing or caulking of cracks and the like. One component and two component hardenable compositions are known in the art as shown for example in U.S. Pat. Nos. 3,122,516, 3,464,951 and 3,334,067 and in British Pat. No. 1,110,429. These prior art documents are relied on herein for their disclosures and incorporated.
Furthermore, the filler of the invention may be used in organopolysiloxane elastomers, hardenable at room temperature as for example, preferably in a two-component silicon printing composition.
According to the invention, the hydrophobic precipitated silicic acid may also be used in hot vulcanizing diorganopolysiloxane elastomers. They may be used for example, as a cable insulation material.
All diorganopolysiloxanes may be used for purposes of the invention which hitherto were used or could be used as the basis for plastic masses hardenable or hardening into organopolysiloxane elastomers at room temperature (RTV) or only slightly higher temperature (LTV) or high temperature (HTV). They are known in the art and may be represented for example, by the general formula:
Z.sub.n Si(R).sub.3-n --O--[Si(R.sub.2)O].sub.x --Si(R).sub.3-n -Z.sub.n
in which R is the same or different monovalent, optionally substituted and/or polymeric hydrocarbon radicals, Z is a hydroxyl group, hydrolyzable group and/or hydrolyzable atom, or in case of there being only masses hardenable at slightly elevated temperature, alkenyl groups, n is 1,2 or 3 and x a whole number with a value of at least 1.
Examples of hydrocarbon radical R are alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl and octyl radicals; alkenyl radicals such as the vinyl, allyl, ethylallyl and butadienyl radical; and aryl radicals such as phenyl and tolyl.
Examples of subtituted hydrocarbon radicals R are especially halogenated hydrocarbon radicals, such as 3,3,3-trifluoropropyl, chlorophenyl and bromotolyl; and cyanoalkyl radicals such as beta-cyanoethyl.
Examples of polymeric (may also be designated as "modifying") substituted and unsubstituted hydrocarbon radicals R, are polystyrl, polyvinylacetyl, polyarylyl, polymethacrylyl and polyacrylic nitrilyl radicals bound to silicon by way of carbon.
At least the majority of the radicals R consist preferably of methyl groups largely because of easier accessability. Any remaining radicals R, are preferably vinyl and/or phenyl groups.
Particularly in case of masses hardenable to elastomers at room temperature in the presence of water and storable under moisture free conditions, Z is generally a hydrolizable group. Examples of such groups are amino, amido, aminoxy, oxime, alkoxy, alkoxyalkoxy--(for example, CH3 OCH2 CH2 O--), alkenyloxy-(for example, H2 C═(CH3)CO--), acyloxy and phosphato groups. Above all, acetoxy groups are preferred as the Z acyloxy group, chiefly because of their easier accessability. However, for example, when Z is an oxime group such as those of the formula --ON═C(CH3) (C2 H5), excellent results will be achieved.
Examples of hydrolyzable atoms Z are halogen and hydrogen atoms. Examples of alkenyl groups Z are especially vinyl groups. It should be noted that the same or different Z groups may be bound to an Si-atom. Mixtures of different diorganopolysiloxanes may be used.
According to the invention, masses hardenable to elastomers, especially with exclusion of water, and in the case of admission of water, masses hardening to elastomers at room temperature can be produced from the hydrophobic silicic acid described herein, by mixing the diorganopolysiloxanes and possibly additional substances at room temperature or at only slightly elevated temperature, optionally after addition of crosslinking agents. This mixing may be accomplished in any known manner, as for example in mechanical mixing devices.
Preferably the fillers used according to the invention are used in quantities of 5 to 50% by weight, related to the total weight of the masses hardenable to elastomers. In the case of HTV organo polysiloxane elastomers, from 5 to 50% by weight may be used. In case of RTV organopolysiloxane elastomers, from 5 to 35 preferably 5 to 25% by weight may be used.
Whenever, as sole terminal units capable of reacting only such units with Si-bound hydroxyl groups are present in the diorganopolysiloxanes, containing terminal units capable of reactions, then these diorganopolysiloxanes, in order to harden them in a per se known manner, or in order to convert them into compounds hardening to elastomers by the water contained in the air, optionally with the addition of more water, must be converted with crosslinking agents, and further optionally in the presence of a condensation catalyst in a known manner. In case of HTV-diorganopolysiloxane elastomers, one may use, in case of correspondingly high temperatures, organic peroxides, such as for example, bis-2.4 dichlorobenzoyl peroxide, benzoylperoxide, dicumylperoxide, tertiary butylperbenzoate or tert. butylperacetate as a crosslinking agent.
As hot volcanizing organosiloxanes one may use such substances wherein the organic substituents of which consist of methyl, ethyl, phenyl, trifluoromethyl phenyl[F3 CC6 H4 ], or trimethyl silmethyl radicals [(CH3)3 SiCH2 --], for example, dimethyl, diethyl, phenyl, methyl, phenylethyl, ethylmethyl, trimethylsilylmethylene methyl, trimethylsilylmethylene ethyl, trifluoromethylphenylmethyl, or trifluoromethylphenylethyl siloxane or copolymerisates of such compounds. In addition the polymerisates may contain limited quantities of diphenylsiloxane, bis-trimethylsilyl methylene siloxane, bis-trifluoromethyl phenylsiloxane units as well as siloxanes with units of the formula RSiO1.5 and R3 SiO0.5, whereby R represents one of the above radicals.
Examples for crosslinking agents are particularly silanes of the general formula:
R.sub.4-t SiZ'.sub.t'
in which R has the meaning stated above, Z', is a hydrolizable group and/or a hydrolizable atom and t is 3 or 4. The previously mentioned examples for hydrolizable groups Z and hydrolizable atoms Z apply equally for the hydrolizable groups Z' and the hydrolizable atoms Z'.
Examples of silanes of the above formula are methyl triacetoxysilane, isopropyl triacetoxysilane, isopropoxy triacetoxysilane, vinyltriacetoxysilane, methyl trisdiethylamino oxysilane, methyl tris (-cyclohexylamino)-silane, methyltris (-diethylphosphate)-silane and methyltris (-methylethylketoximo)-silane.
Furthermore, for example, polysiloxanes, which contain at least 3 Z' groups or atoms per molecule, may also be used instead of or mixed with silances of the above formula, whereby the silicon valencies not saturated by Z' group or atoms, are saturated by siloxane oxygen atoms and optionally R groups. The best known examples of crosslinking agents of the latter type are the polyethylsilicates with an SiO2 content of about 40% by weight, hexaethoxydisiloxane and methane polysiloxane.
The best known examples for condensation catalysts are tin salts of fatty acids, such as dibutyltindilaurate, dibutyltindiacetate and tin-(II)-octoate.
Whenever units with alkenyl groups are present as the only reactive terminal units in the diorganopolysiloxanes containing reactive terminal units, then the hardening into elastomers may take place in a known manner with organopolysiloxanes, which contain on an average at least 3 Si-bound hydrogen atoms per molecule, such as methanepolysiloxane, in the presence of catalysts, such as platinum-(IV)-chloricacid, promoting the addition of alkenyl group to Si-bound hydrogen. In that case there are at room temperature or at only slightly higher temperature (mostly 50° to 80° C.) hardenable (LTV) masses available.
Finally, as an other example for the hardening into elastomers there should be mentioned the use of polycyclic organopolysiloxanes in the presence of equilibration catalysts, such as phosphorus nitrile chlorides.
Naturally, the masses hardenable into elastomers, beside diorganopolysiloxanes, precipitated silicic acid according to the invention, crosslinking agents and crosslinking catalysts, may optionally contain conventional fillers used in masses hardenable into elastomers. Examples of such substances are fillers with a surface area less than 50 m2 /g, such as quartz powder, diatomaceous earth, zirconium silicate and calcium carbonate, untreated, pyrogenic silicondioxide, organic resins such as polyvinylchloride powder, organopolysiloxane resins, fibrous fillers such as asbestos, glass fibers and organic fibers, pigments, soluble dyes, aromatics, corrosion inhibitors, agents stabilizing the masses against the effect of water, such as acetic acid anhydride, agents for delaying or retarding the hardening or curing, such a benzotriazole and softeners, such as dimethylpolysiloxanes, endblocked by trimethyl siloxy groups.
The above enumerated combination of physico-chemical data relating to the hydrophobic precipitated silicic acid of the invention, because of its excellent dispersability will lead to a highly effective reinforcing and strengthening filler. The aquilibrium moisture content, clearly reduced as compared to known precipitated silicic acids, produces advantages during processing, for example in the case of pressureless vulcanization where a cured product is obtained with fewer bubbles as compared to the use of the known hydrated precipitated silicic acid. The electrolyte content combined with the low moisture content leads to good electrical characteristics in the cured product. In cold-hard-enable silicon-rubber sealing masses, the hydrophobic precipitated silicic acid of the invention, on the basis of its low water content, exhibits advantages in storage stability of the un-cured masses.
The production of and the physico-chemical data and the use of the hydrophobic precipitated silicic acid of the invention will be explained and described in more detail on the basis of the following illustrative examples:
EXAMPLE 1
Production of the original precipitation suspension of a hydrophylic silicic acid for the subsequent wet hydrophobation.
50.0 m3 of water are put into a reaction vessel. Slowly, 9.2 m3 of sodium silicate solution and 0.9 m3 H2 SO4 are added to the vessel while stirring, whereby an alkaline pH value is maintained in the mixture during the addition. After completing the addition of sodium silicate and H2 SO4 the pH value of the suspension obtained lies within the alkaline range.
For the determination of the physical and chemical properties of the hydrophylic silicic acid, a part of the suspension is filtered off, washed until "poor in electrolyte," subsequently dryed in the drying cabinet at 105° C. up to constant weight and is ground in a disk mill.
The hydrophylic silicic acid obtained has the following physico-chemical characteristic data:
______________________________________                                    
BET-surface according to                                                  
                  m.sup.2 /g 155                                          
 DIN 66 131                                                               
Average size of primary                                                   
 particles from EM-                                                       
                  mμ(nm)  18 - 20                                      
 records                                                                  
Loss at drying according                                                  
 to DIN 55 921 after                                                      
                  %          3.0                                          
 2 hrs at 105° C.                                                  
Loss at red heat (related                                                 
 to substance dried for                                                   
 2 hrs at 105° C.) accord-                                         
                  %          3.3                                          
 ing to DIN 55 921                                                        
pH value (in 5% aqueous                                                   
 suspension) accord-         7.7                                          
 ing to DIN 53 200                                                        
Conductivity (in 4%                                                       
 aqueous suspension)                                                      
                  μS      240                                          
Tamping density of the                                                    
 unaerated substance                                                      
                  g/l        140                                          
 according to DIN 53                                                      
 194                                                                      
SO.sub.2 content (related to                                              
 the substance dried                                                      
                  %          0.22                                         
 2 hrs at 105° C.)                                                 
Na.sub.2 O content (related                                               
 to the substance %          0.18                                         
 dried 2 hrs at                                                           
 105° C.)                                                          
______________________________________
METHOD FOR THE DETERMINATION OF THE ELECTRIC CONDUCTIVITY
A sample of 4.0 silicic acid is heated in 50 ml fully desalinated water in a 150 ml glass beaker and is boiled for one minute while stirring. Subsequently, the suspension is transferred into a 100 ml measuring flask, is cooled down, and is then filled up to the mark with fully desalinated water. After agitating, the measuring cell of the conductivity measuring device is first preliminarily flushed with the suspension to be measured and is then filled or the measuring cell is submerged into the suspension. The electric conductivity is read from the measuring device and the temperature of the suspension is determined during the measurement.
Calculation: The electric conductivity is given in μS related to 20° C.
EXAMPLE 2
Production of a hydrophobic precipitated silicic acid of the invention obtained by wet hydrophobing.
While maintaining a pH value of the suspension of 8.5, 193 g. of dimethyldichlorosilane are added under intensive stirring during a time of 30 minutes to 10 l. of an original aqueous suspension of silicic acid according to example 1 with a solid concentration of 57.9 g/l. After a subsequent mixing time of 60 minutes the precipitated silicic acid, covered (coated) at 25% with dimethylchlorosilane, is separated, is dryed at 105° C., tempered at 350° C. for 2.0 hrs, and subsequently ground.
The hydrophobic precipitated silicic acid thus obtained, has the following physico-chemical characteristics:
______________________________________                                    
Loss at red heat at                                                       
                   %          5.5                                         
 1000° C. according                                                
 to DIN 55 921                                                            
Of this, moisture at                                                      
                   %          0.4                                         
 105° C. according                                                 
 to DIN 55 921                                                            
pH value according to         8.0                                         
 DIN 53 200                                                               
BET-surface according                                                     
                   m.sup.2 /g 89                                          
 to DIN 66 131                                                            
Wettability with water                                                    
                   %          0.05                                        
Conductivity       μ S     160                                         
C - content        %          2.2                                         
Water absorption at                                                       
 30° C. and 30% RH                                                 
                   %          1.2                                         
 at 30° C. and 70% RH                                              
                   %          2.0                                         
Tamping density of the                                                    
                   g/l        130                                         
 unaerated substance                                                      
 according to DIN 53                                                      
 194                                                                      
______________________________________
DETERMINATION OF THE WATER-WETTABILITY OF HYDROPHOBIC SILICIC ACIDS
The determination of the water-wettable parts of hydrophobic silicic acid is described in the following method of analysis.
CARRYING OUT THE DETERMINATION
0.2 g of hydrophobic silicic acid are placed with 50 ml of distilled water into a 250 ml vibrating funnel and are vibrated at the highest speed for 1 minute with the help of a Turbula-mixer.
After short settling of the wetted parts, 45 ml of the suspension after cautious agitation are drained into an evaporating pan, are evaporated on a waterbath and are then dryed at 105° C. ##EQU1##
DETERMINATION OF MOISTURE ABSORPTION
In case of the determination of the moisture absorption the maximum or time-dependent moisture absorption of silicic acids is determined in dependence on the temperature and of the relative humidity of the air.
METHOD FOR THE DETERMINATION
A silicic acid sample of about 2.5 g is weighed in up to 0.1 mg. exactly, into a dry calibrated weighing bottle and is dried for 2 hours at 105° C. After cooling, the weight is determined on an analytical balance. Subsequently, the open weighing bottle is kept with the sample in a conditioning cabinet at a predetermined temperature and relative humidity of the air. One may then either determine a moisture absorption/time diagram or the maximum moisture absorption.
Customarily the determination is made at
30° C. and 30% relative humidity of the air
30° C. and 70% relative humidity of the air ##EQU2##
EXAMPLE 3
Use of a hydrophobic precipitated silicic acid of the invention in cold hardening 1--component silicon rubber masses.
In this example the hydrophobic precipitated silicic acid of the invention according to example 2, is tested as a reinforcing filler and thixotroping agent in a 1-component silicon rubber crack-sealing mass (cold curing).
In case of these experiments, the silicic acid Aerosil 150R of the Degussa Company as well as the commercial product HDK H2000 of the Wacker Company were used for comparison in the same silicon rubber mass.
HDK H2000R is a highly dispersed silicic acid, which is produced by flame-hydrolysis from volatile silicon masses and is subsequently hydrophobed by reaction with organosilanes. It is therefore tightly covered with trimethylsilyl groups on the surface and has the following physico-chemical characteristics:
______________________________________                                    
Surface according to                                                      
 BET              m.sup.2 /g  170 ± 30                                 
SiO.sub.2 content % by weight >97                                         
Bulk weight unpressed                                                     
                  g/l         about 90                                    
Moisture according to                                                     
 DIN 53 198 Process                                                       
                  % by weight <0.6                                        
 (Verf.) A 2 hrs at                                                       
 105° C.                                                           
Loss at red heat accord-                                                  
 ing to DIN 52 911 2                                                      
                  % by weight <2.5                                        
 hrs at 1000° C.                                                   
pH value according to                                                     
 DIN 53 200 in 4%             6.7-7.7                                     
 dispersion in water-                                                     
 methanol = 1:1                                                           
Grit according to Mocker                                                  
                  % by weight <0.05                                       
 (Din 53 580)                                                             
Adhering (retained) HCL                                                   
                  % by weight <0.020                                      
Al.sub.2 O.sub.3  % by weight <0.05                                       
Fe.sub.2 O.sub.3  % by weight <0.005                                      
TiO.sub.2         % by weight <0.003                                      
C                 % by weight <3                                          
______________________________________
Aerosil 150R is a pyrogenically produced silicic acid with the following physico-chemical characteristics.
______________________________________                                    
Surface According                                                         
to BET             m.sup.2 /g 150 ± 50                                 
Average size of the                                                       
primary particles  mμ (nm) 14                                          
Loss at drying (DIN                                                       
 53 198/A) (2 hrs             0.5                                         
 at 105° C.)                                                       
Loss at red heat (DIN                                                     
 52 911) (2 hrs at            1                                           
 1000° C.)                                                         
pH value (DIN 53 200)                                                     
 (in 4% aqueous               3.6-4.5                                     
 dispersion)                                                              
SiO.sub.2 *        %          99.8                                        
Al.sub.2 O.sub.3   %          0.05                                        
Fe.sub.2 O.sub.3   %          0.003                                       
TiO.sub.2          %          0.03                                        
HCL                %          0.025                                       
Grit according to                                                         
 Mocker (DIN 53    %          0.05                                        
 580)                                                                     
Wetting behavior              hydrophylic                                 
______________________________________                                    
  *related to the substance roasted 2 hours at 1000° C.
At the same time the following formula with acetate hardener was used as the base composition:
______________________________________                                    
68.4 parts by weight                                                      
               dimethylpolydiloxane with hydro-                           
               xyl terminal groups viscosity                              
               50,000 cSt.                                                
271 parts by weight                                                       
               dimethylpolysiloxane with tri-                             
               methyl siloxy terminal groups vis-                         
               cosity 1000 cST                                            
4.5 parts by weight                                                       
               methyltriacetoxysilane (cross-                             
               linking agent)                                             
0.0005 pts. by weight                                                     
               dibutyltindiacetate                                        
plus silicic acid                                                         
to be tested.                                                             
______________________________________
The incorporation of the silicic acid takes place after the addition of the crosslinking agent in an evacuated planetary type mixer.
The paste-like crack-sealing mass or its vulcanisate cured (hardened) for 7 days in the air was then subjected to the following tests:
(a) Extrusion capacity according to ASTM 2452-69
staying power according to the "cap method" (Hutchenmethods)
(c) modulus at 100% expansion according to DIN 53 504
(d) tensile strength according to DIN 53 504
(e) breaking tension according to DIN 53 504
(f) resistance against further tearing according to DIN 53 515
(g) Shore-A-hardeness according to DIN 53 505
The results of these investigations are combined in the following table I. At the same time, the following technical progress may be ascertained as compared to the known pyrogenic silicic acids Aerosil 150 as well as the hydrophobic silicic acid HDK H2000:
Aerosil 150 may only be incorporated up to 8% into the 1-component sealing mass. A higher degree of filling leads to a mass difficult to process. The level of the machanical data attainable at a degree of 8% filler content corresponds to the customary status of the prior art.
On the contrary with the silicic acid of the invention according to example 2 and with a content of 20% filler an essentially higher level of the mechanical data will be achieved, which satisfy the requirements made of highstrength sealing masses. The extrusion of the mass has been fully satisfied at this level of filler content. The stability in storage is good too.
On the other hand in the case of a filler content of 20% the level of values of the mechanical data of the commercial product HDK H2000, which represents the latest status of the prior art, is not comparable to that of the cured products (vulcanizates) containing the precipitated silicic acid of the invention. This is particularly true for the tensile strength and the elongation at break, which both lie 45% below the corresponding values of the silicic acid of the invention. Only in case of an increase of the filler content to 25% may the data for HDK H2000 by considered comparable.
Surprisingly, it was thus found that with the use of only 20% of the precipitated silicic acid a clearly improved set of characteristics (compared to 25% HDK H2000) may be achieved. Moreover, because of the noticeably low production costs as compared to pyrogenic hydrophobic silicic acid, additional possibilities of application will be opened up thereby.
TABLE I
Comparison of a hydrophobic precipitated silicic acid of the invention according to example 2 in a 1-component silicon sealing mass with pyrogenic silicic acid of the prior art.Type of silicic storage (Huetchen Extrudabilityacid (%)* life method) (g/min)______________________________________silicic acidaccording to 20 good good 8.2 after 0 daysexample 2 8.0 after 28 daysAerosil 150 8 good good 8 after 0 days 8 after 28 daysHDK H2000 20 good good 19 after 0 days 22 after 28 daysHDK H2000 25 good good 11 after 0 days 9 after 28 days______________________________________ Resis- tance against con- Elong- tinuedType Modulus Tensile ation at tear- Shoreof silicic acid 100 Strength break ing (N/ hard-Type (%)* (N/mm2) (N/mm) (%) mm) iness______________________________________Silicic acidAccording toExample 2 20 4.6 45 780 16 18Aerosil 150 8 3.0 10 400 2.5 20HDK H2000 20 5.0 25 430 15 24HDK H2000 25 6.0 45 490 18 32______________________________________ *% by weight, related to total mixture
EXAMPLE 4 Production of a hydrophobic precipitated silicic acid of the invention, obtained by wet hydrophobing
While maintaining a pH value of the suspension of 8.5, 175.6 g of dimethyldichlorosilane are added under intensive stirring during a time of 30 minutes to 12 l. of an original aqueous suspension of the silicic acid according to example 1, with a solids concentration of 57.9 g/l. After a subsequent mixing time of 60 minutes the precipitated silic acid, covered at 20% with dimethyldichlorosilane, is dried at 105° C., is tempered at 350° C. for 1.5 hours and is subsequently ground up. The precipitated silicic acid has the following physico-chemical characteristics:
______________________________________                                    
Loss at red heat at                                                       
 1000° C. according                                                
                   %          5.5                                         
 to DIN 55 921                                                            
Of this the humidity                                                      
 at 105° C. according                                              
                   %          0.4                                         
 to DIN 55 921 is                                                         
pH value according to         7.5                                         
 DIN 53 200                                                               
BET-surface according                                                     
 to DIN 66 131     m.sup.2 /g 94                                          
Water-wetability              0.06                                        
Conductivity       μS      92                                          
C-Content          %          2.1                                         
Water absorption at                                                       
 30° C. and 30% RH                                                 
                   %          1.3                                         
at 30° C. and 70% RH                                               
                   %          2.0                                         
Tamping density of                                                        
 the unaerated                                                            
 substance accord- g/l        137                                         
 ing to DIN 53 194                                                        
______________________________________
EXAMPLE 5
Use of a hydrophobic precipitated silicic acid in cable masses according to the invention on the basis of organopolysilicones.
In this example the hydrophobic precipitated silicic acid of example 4 according to the invention is incorporated as reinforcing filler in hot vulcanized silicon rubber and is checked for the electric volume resistance of the cured goods produced therewith.
Owing to its excellent dielectric characteristics, hot-vulcanizing silicon rubber is also used as a high grade cable insulating material. In this case, highly active pyrogenic silicic acid is conventionally used as a filler because of it unity and its favorable dielectric characteristics. It has been known, that the insulating characteristics are improved further, whenever the fully cured compounds are further subjected to an extended tempering process (at least 6 hours) at elevated temperatures (200° C.).
In this test, the following formula was used:
______________________________________                                    
100 parts by weight                                                       
               of dimethylpolysiloxane with                               
               trimethyl siloxy terminal groups                           
               as well as with a content of                               
               vinyl groups                                               
40 parts by weight                                                        
               of silicic acid                                            
1.4 parts by weight                                                       
               of bis-2.4-dichlorobenzoylper-                             
               oxide (50% as paste in silicon                             
               oil)                                                       
Vulcanization: 7 min. at 130° C.                                   
Tempering:     0 or 6 hrs. at 200° C.                              
Conditioning:  24 hours at 22° C. and 80% rela-                    
               tive humidity of the air                                   
______________________________________
The results of the comparison with Aerosil 200®*, a pyrogenic silicic acid sold by Degussa are shown in FIG. 1. As is clear from the curves, it is possible to achieve surprisingly similarly good results with precipitated silicic acid of the invention, as with the pyrogenic silicic acid. Furthermore it was found surprisingly, that the good electrical characteristics may also be achieved with the silicic acid of the invention even without the above mentioned expensive tempering process. Beside the more favorable production costs, this represents another advantage of the precipitated silicic acid of the invention.
______________________________________                                    
Surface according                                                         
                 m.sup.2 /g   200 ± 25                                 
 to BET                                                                   
Average size of                                                           
 the primary     mμ        12                                          
 particles                                                                
Tamping volume                                                            
 (DIN 53 194)    ml/100g      1700                                        
Compacted goods  ml/100g      1000                                        
Loss at drying                                                            
 (DIN 53 198,                                                             
 type A) 2 hrs   % by weight  <1.5                                        
 at 105° C.                                                        
Loss at red heat                                                          
 (DIN 52 911)    % by weight  <1.5                                        
 2 hrs at                                                                 
 1000° C.                                                          
pH value (DIN 53                                                          
 200) in 4%                                                               
 aqueous dis-                 3.6 - 4.3                                   
 persion                                                                  
SiO.sub.2        % by weight  >99.8                                       
Al.sub.2 O.sub.3 % by weight  <0.05                                       
Fe.sub.2 O.sub.3 % by weight  <0.003                                      
TiO.sub.2        % by weight  <0.03                                       
HCl              % by weight  <0.025                                      
Grit according                                                            
 to Mocker       % by weight  0.05                                        
 (DIN 53 580)                                                             
______________________________________
Further embodiments, variations and modificitions of the invention will be apparent to those skilled in the art.

Claims (6)

We claim:
1. Hydrophobic precipitated silicic acid, having the following characteristics
______________________________________                                    
BET-Surface according to                                                  
                    m.sup.2 /g                                            
                             110 ± 40                                  
 DIN 66 131                                                               
Average size of the pri-                                                  
 mary particles from                                                      
                    mμ (nm)                                            
                             15-22                                        
 EM records                                                               
Losses in weight at dry-                                                  
 ing according to DIN                                                     
                    %        <2.5                                         
 55 921 after 2 hrs at                                                    
 105 ° C.                                                          
Weight loss at red heat                                                   
 (related to the sub-                                                     
 stance dryed 2 hrs at                                                    
                    %        5.5 ± 1.5                                 
 105° C. according to DIN                                          
 55 921                                                                   
pH value (in 5% aqueous                                                   
 methanolic suspension)      7.5 ± 1.0                                 
 according to DIN 53 200                                                  
Conductivity (in 4% aqueous                                               
 methanolic suspension)                                                   
                    μS    <600                                         
Tamping density of the un-                                                
 aerated substance accord-                                                
                    g/l      130 ± 40                                  
 ing to DIN 53 194                                                        
Wettability with water       <0.1                                         
Carbon content      %        2.5 ± 0.6                                 
Water absorption at 30 ° C. and                                    
 30% RH (relative humidity)                                               
                    %        1.2 ± 0.4                                 
 at 30 ° C. amd 70% RH                                             
                    %        1.5 ± 0.5                                 
______________________________________
2. A process for the production of hydrophobic precipitated silicic acid having the characteristics as defined in claim 1, comprising introducing a hydrophobic producing material into an original aqueous suspension of hydrophilic silicic acid having the following physico-chemical characteristics, which characteristics are determined after separation from the precipitation solution, intensive washing with water and an period of drying of the hydrophylic precipitated silicic acid:
______________________________________                                    
BET surface according                                                     
                  m.sup.2 /g 160 ± 40                                  
 to DIN 66 131                                                            
Average size of the                                                       
 primary particles                                                        
                  mμ (nm) 14-22                                        
 from EM records                                                          
Losses in weight at                                                       
 drying according %          2.5-4.0                                      
 to DIN 55 921                                                            
 after 2 hrs at                                                           
 105° C.                                                           
Loss at red heat                                                          
 (related to the                                                          
 substance dryed  %          3.5 ± 1.0                                 
 2 hrs at 105° C.)                                                 
 according to DIN                                                         
 55 921                                                                   
pH value (in 5% aqueous      7.0-8.5                                      
 suspension) accord-                                                      
 ing to DIN 53 200                                                        
Conductivity (in 4%                                                       
 aqueous suspension)                                                      
                  μ S     <600                                         
Tamping density of the                                                    
 unaerated substance                                                      
                  g/l        140 ± 40                                  
 according to DIN 53                                                      
 194                                                                      
SO.sub.3 content (related to                                              
 the substance dryed                                                      
                  %          <0.3                                         
 2 hrs at 105° C.)                                                 
Na.sub.2 O content (related to                                            
 the substance dryed 2                                                    
                  %          <0.3                                         
 hrs at 105° C.)                                                   
______________________________________
while maintaining an alkaline pH value to obtain a mixture, stirring the mixture thus obtained, separating the hydrophobic precipitated silicic acid, tempering the hydrophobic product obtained, for 60 to 180 minutes, at a temperature of 200°-400° C. and finely dividing the product.
3. Hardenable elastomeric composition comprising an elastomer and the precipitated silicic acid as defined in claim 1 in an amount to produce a strengthening effect in said elastomer.
4. A hardenable elastomeric composition as defined in claim 3 wherein said elastomer is formed from a diorgano polysiloxane.
5. A sealing or caulking composition comprising a silicone rubber and precipitated silicic acid as defined in claim 1, in a sufficient amount to act as a strengthening filler in ad-mixture with said silicone rubber.
6. A cable formed of a rubber composition comprising a silicone rubber containing the precipitated silicic acid as defined in claim 1 as a reinforcing filler.
US05/920,515 1978-06-29 1978-06-29 Hydrophobic precipitated silicic acid and compositions containing same Expired - Lifetime US4208316A (en)

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WO1981003485A1 (en) * 1980-06-03 1981-12-10 Dow Corning Method for producing hydrophobic reinforcing silica fillers and fillers obtained thereby
US4359342A (en) * 1981-01-28 1982-11-16 Phillips Petroleum Company Silica reinforced rubber
EP0238876A2 (en) * 1986-02-26 1987-09-30 Toray Silicone Company, Ltd. Silica-containing polyorganosiloxane compositions
EP0306862A2 (en) * 1987-09-10 1989-03-15 Dow Corning Corporation Method of hydrophobing silica
US4849022A (en) * 1986-06-25 1989-07-18 Toray Silicone Co., Ltd. Method for modifying the surface of finely divided silica
US4920457A (en) * 1988-01-12 1990-04-24 Siemens Aktiengesellschaft Aluminum electrolyte capacitor and method for the manufacture thereof
US4950502A (en) * 1987-09-10 1990-08-21 Dow Corning Corporation Method of hydrophobing silica
US5057151A (en) * 1988-11-25 1991-10-15 Wacker-Chemie Gmbh Process for preparing hydrophobic particulate solids containing si-oh groups and a process for using the same
US5183710A (en) * 1990-08-30 1993-02-02 U-Sus Distributors, Inc. Hydrophobic inorganic materials and process for making same
US5429873A (en) * 1990-07-19 1995-07-04 Degussa Aktiengesellschaft Surface-modified silicon dioxides
US5446075A (en) * 1993-04-01 1995-08-29 Jmk International, Inc. Monitor putty
US5472994A (en) * 1993-04-01 1995-12-05 Jmk International, Inc. Microwave-heatable exercise putty
US5591797A (en) * 1993-10-25 1997-01-07 Wacker-Chemie Gmbh Transition metal-containing hydrophobic silica
EP0807509A1 (en) * 1996-05-02 1997-11-19 Wacker-Chemie GmbH Continuous process for making storage stable organopolysiloxane compositions
EP0808880A2 (en) * 1996-04-26 1997-11-26 Degussa Aktiengesellschaft Silanized silicas
US5693689A (en) * 1993-04-01 1997-12-02 Jmk International, Inc. Monitor putty with increasing stiffness
US5908660A (en) * 1997-09-03 1999-06-01 Dow Corning Corporation Method of preparing hydrophobic precipitated silica
WO1999036479A1 (en) * 1998-01-15 1999-07-22 Cabot Corporation Method of preparing organically modified silica
US6051672A (en) * 1998-08-24 2000-04-18 Dow Corning Corporation Method for making hydrophobic non-aggregated colloidal silica
US6090439A (en) * 1998-01-15 2000-07-18 Cabot Corporation Method of preparing treated silica
US6107351A (en) * 1997-02-24 2000-08-22 Dow Corning Corporation Neutral-aged hydrophobic silica gels with reduced surface area
US6159540A (en) * 1998-01-15 2000-12-12 Cabot Corporation Polyfunctional organosilane treatment of silica
US6174926B1 (en) 1999-01-13 2001-01-16 Cabot Corporation Method of preparing organically modified silica
US6193795B1 (en) 1993-08-02 2001-02-27 Degussa Corporation Low structure pyrogenic hydrophilic and hydrophobic metallic oxides, production and use
US6197384B1 (en) * 1998-06-25 2001-03-06 Degussa-Huls Ag Hydrophobic precipitated silica
US20010034375A1 (en) * 1996-11-26 2001-10-25 Fritz Schwertfeger Organically modified aerogels, processes for their preparation by surface modification of the aqueous gel, without prior solvent exchange, and subsequent drying, and thier use
US20020032272A1 (en) * 1998-06-05 2002-03-14 Werner Sievers Nanoporous interpenetrating organic-inorganic networks
US20020040661A1 (en) * 2000-04-11 2002-04-11 Degussa Ag Coatings for inkjet media
US6579929B1 (en) 2000-01-19 2003-06-17 Bridgestone Corporation Stabilized silica and method of making and using the same
US20030124045A1 (en) * 2001-12-28 2003-07-03 Nippon Aerosil Co., Ltd. Low viscosity-increment fumed-silica and its slurry
EP1431245A1 (en) * 2002-12-17 2004-06-23 Degussa-Hüls Aktiengesellschaft Surface modified structural silica of aerogel-type
US20040120876A1 (en) * 2002-12-18 2004-06-24 Degussa Ag Surface-modified, aerogel-type structured silica
US20060171872A1 (en) * 2004-10-20 2006-08-03 Cabot Corporation Method of preparing hydrophobic silica directly from an aqueous colloidal silica dispersion
US7618349B1 (en) 2006-02-02 2009-11-17 Aaron Muderick Therapeutic putty with increasing or decreasing stiffness
CN102391296A (en) * 2011-07-13 2012-03-28 东营旭业化工有限公司 Preparation method of hydrophobic silane dispersing agent
EP2220172B1 (en) 2007-12-19 2016-03-02 Wacker Chemie AG Hydrophobicization of silicas under oxidizing conditions

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US2802850A (en) * 1954-11-01 1957-08-13 Gen Electric Hydrophobic silicas
US3656981A (en) * 1966-06-18 1972-04-18 Degussa Production of finely divided organically modified silicas
US3677784A (en) * 1969-01-27 1972-07-18 Wacker Chemie Gmbh Method for preparing hydrophobic silica
US3904787A (en) * 1972-08-31 1975-09-09 Degussa Process for hydrophobization of silicates
US3847848A (en) * 1972-12-04 1974-11-12 Gen Electric Two-part room temperature vulcanizable silicone rubber compositions
US4072796A (en) * 1974-07-25 1978-02-07 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for hydrophobization of finely divided silica and silicates using prepolycondensed organosilane
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Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042208A2 (en) * 1980-06-03 1981-12-23 Dow Corning Corporation Method for producing hydrophobic reinforcing silica fillers
EP0042208A3 (en) * 1980-06-03 1981-12-30 Dow Corning Corporation Method for producing hydrophobic reinforcing silica fillers and fillers obtained thereby
US4344800A (en) * 1980-06-03 1982-08-17 Dow Corning Corporation Method for producing hydrophobic reinforcing silica fillers and fillers obtained thereby
WO1981003485A1 (en) * 1980-06-03 1981-12-10 Dow Corning Method for producing hydrophobic reinforcing silica fillers and fillers obtained thereby
US4359342A (en) * 1981-01-28 1982-11-16 Phillips Petroleum Company Silica reinforced rubber
EP0238876A3 (en) * 1986-02-26 1990-02-07 Toray Silicone Company, Ltd. Silica-containing polyorganosiloxane compositions
EP0238876A2 (en) * 1986-02-26 1987-09-30 Toray Silicone Company, Ltd. Silica-containing polyorganosiloxane compositions
US4849022A (en) * 1986-06-25 1989-07-18 Toray Silicone Co., Ltd. Method for modifying the surface of finely divided silica
EP0306862A2 (en) * 1987-09-10 1989-03-15 Dow Corning Corporation Method of hydrophobing silica
US4950502A (en) * 1987-09-10 1990-08-21 Dow Corning Corporation Method of hydrophobing silica
EP0306862A3 (en) * 1987-09-10 1990-12-27 Dow Corning Corporation Method of hydrophobing silica
US4920457A (en) * 1988-01-12 1990-04-24 Siemens Aktiengesellschaft Aluminum electrolyte capacitor and method for the manufacture thereof
US5057151A (en) * 1988-11-25 1991-10-15 Wacker-Chemie Gmbh Process for preparing hydrophobic particulate solids containing si-oh groups and a process for using the same
US5429873A (en) * 1990-07-19 1995-07-04 Degussa Aktiengesellschaft Surface-modified silicon dioxides
US5183710A (en) * 1990-08-30 1993-02-02 U-Sus Distributors, Inc. Hydrophobic inorganic materials and process for making same
US5693689A (en) * 1993-04-01 1997-12-02 Jmk International, Inc. Monitor putty with increasing stiffness
US5472994A (en) * 1993-04-01 1995-12-05 Jmk International, Inc. Microwave-heatable exercise putty
US5446075A (en) * 1993-04-01 1995-08-29 Jmk International, Inc. Monitor putty
US6193795B1 (en) 1993-08-02 2001-02-27 Degussa Corporation Low structure pyrogenic hydrophilic and hydrophobic metallic oxides, production and use
US5591797A (en) * 1993-10-25 1997-01-07 Wacker-Chemie Gmbh Transition metal-containing hydrophobic silica
EP0808880A2 (en) * 1996-04-26 1997-11-26 Degussa Aktiengesellschaft Silanized silicas
EP0808880A3 (en) * 1996-04-26 1999-10-27 Degussa-Hüls Aktiengesellschaft Silanized silicas
EP0807509A1 (en) * 1996-05-02 1997-11-19 Wacker-Chemie GmbH Continuous process for making storage stable organopolysiloxane compositions
US5854343A (en) * 1996-05-02 1998-12-29 Wacker-Chemie Gmbh Continuous process for preparing storage-stable organopolysiloxane compositions
US7470725B2 (en) 1996-11-26 2008-12-30 Cabot Corporation Organically modified aerogels, processes for their preparation by surface modification of the aqueous gel, without prior solvent exchange, and subsequent drying, and their use
US20010034375A1 (en) * 1996-11-26 2001-10-25 Fritz Schwertfeger Organically modified aerogels, processes for their preparation by surface modification of the aqueous gel, without prior solvent exchange, and subsequent drying, and thier use
US6107351A (en) * 1997-02-24 2000-08-22 Dow Corning Corporation Neutral-aged hydrophobic silica gels with reduced surface area
US5908660A (en) * 1997-09-03 1999-06-01 Dow Corning Corporation Method of preparing hydrophobic precipitated silica
WO1999036479A1 (en) * 1998-01-15 1999-07-22 Cabot Corporation Method of preparing organically modified silica
US6159540A (en) * 1998-01-15 2000-12-12 Cabot Corporation Polyfunctional organosilane treatment of silica
US6090439A (en) * 1998-01-15 2000-07-18 Cabot Corporation Method of preparing treated silica
US6825260B2 (en) 1998-06-05 2004-11-30 Cabot Corporation Nanoporous interpenetrating organic-inorganic networks
US20020032272A1 (en) * 1998-06-05 2002-03-14 Werner Sievers Nanoporous interpenetrating organic-inorganic networks
US6197384B1 (en) * 1998-06-25 2001-03-06 Degussa-Huls Ag Hydrophobic precipitated silica
US6051672A (en) * 1998-08-24 2000-04-18 Dow Corning Corporation Method for making hydrophobic non-aggregated colloidal silica
US6174926B1 (en) 1999-01-13 2001-01-16 Cabot Corporation Method of preparing organically modified silica
US6579929B1 (en) 2000-01-19 2003-06-17 Bridgestone Corporation Stabilized silica and method of making and using the same
US20020040661A1 (en) * 2000-04-11 2002-04-11 Degussa Ag Coatings for inkjet media
US6840992B2 (en) 2000-04-11 2005-01-11 Degussa Ag Coatings for inkjet media
US7255843B2 (en) * 2001-12-28 2007-08-14 Nippon Aerosil Co., Ltd. Low viscosity-increment fumed-silica and its slurry
US20030124045A1 (en) * 2001-12-28 2003-07-03 Nippon Aerosil Co., Ltd. Low viscosity-increment fumed-silica and its slurry
EP1431245A1 (en) * 2002-12-17 2004-06-23 Degussa-Hüls Aktiengesellschaft Surface modified structural silica of aerogel-type
US20040120876A1 (en) * 2002-12-18 2004-06-24 Degussa Ag Surface-modified, aerogel-type structured silica
US7402293B2 (en) 2002-12-18 2008-07-22 Degussa Ag Surface-modified, aerogel-type structured silica
US20060171872A1 (en) * 2004-10-20 2006-08-03 Cabot Corporation Method of preparing hydrophobic silica directly from an aqueous colloidal silica dispersion
US7811540B2 (en) 2004-10-20 2010-10-12 Cabot Corporation Method of preparing hydrophobic silica directly from an aqueous colloidal silica dispersion
US7618349B1 (en) 2006-02-02 2009-11-17 Aaron Muderick Therapeutic putty with increasing or decreasing stiffness
EP2220172B1 (en) 2007-12-19 2016-03-02 Wacker Chemie AG Hydrophobicization of silicas under oxidizing conditions
CN102391296A (en) * 2011-07-13 2012-03-28 东营旭业化工有限公司 Preparation method of hydrophobic silane dispersing agent
CN102391296B (en) * 2011-07-13 2014-05-14 山东旭业新材料股份有限公司 Preparation method of hydrophobic silane dispersing agent

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